Water-soluble disazo-dyestuffs



United States Patent ()fiice WATER-SOLUBLE DlSAZO-DYESTUFFS L I WalterNoll, Bad Soden, Taunus, Germany, assiguor to OH Farbwerke HoechstAktiengesellschaft vormals Meister N Lucius & Bruning, Frankfurt amMain, Germany, a 5

corporation of Germany No Drawing. Filed Oct. 15, 1963, Ser. No. 316,432

Claims priority, application Germany, Oct. 19, 1962,

38 093 6 Claims. 61. 260160) (3) The present invention relates to new,very easily Waterin which R has the meaning given above and R representssoluble disazo-dyestufis and to a process for preparing a hydrogen atomor the sulfonic acid group, and by esterithem; more particularly itrelates to disazo-dyestutfs of the fying the disazo-dyestufi so obtainedwith sulfuric acid if general formula (1) R represents a hydrogen atom.

Y Z I l R l l I l l \N/ OH 2 Y HO \N/ SOzCHgCHzO-SO3H SOgCHz-OHO-SO3H inwhich X represents a direct linkage or one of the group- Suitable aminesof the aforementioned general formula ings --O, S, SO; and --CH=CH-- asa (2) are for example:

3O bridge member, Z represents a hydrogen atom or an alkyl 4,4,diaminodipheny1 2 2, disulfonic acid or alkoxy group, Y represents asulfonic acid or carboxylic 4,4I diaminodipheny1 2 2' d b 1i acid aci gup, a R represents a methyl, carboxylic acid or4,4'-diamino-3,3-dimethyl-diphenyl-6,6'-disulfonic acid, carboxyllc acidester g oup. 4,4'-diamino-3,3'-dimethoxydiphenyl-6,6-disulfonic acid,

It has been found, that new, valuable, very easily water- 4,4.'-di i dih 1 th 2,2'-di 1f i id, soluble disaZo-dyestuffs of the general formula(1) 4,4'-diaminodiphenylsulfide-2,2-disulfonic acid,

1| 2 RH N=N- -XN=N |-R N l N \N/ OH z Y HO- N (I I EOrCHr-CHz-O-SOxI-IS|02OH2CH5O-SO3H in which X represents a direct linkage or one of thegroup- 4,4-diaminodiphenyl-sulfone-Z,2'-disulfonic acid, ings O -S--,-SO and CI-I=CH- as a 4,4'-diaminostilbene-2,2-disulfonic acid. bridgemember, Z represents a hydrogen atom or a lower As suitable \azocomponents there may be mentioned alkyl or lower alkoxy group, Yrepresents a sulfonic acid for example: or earboxylic acid group and Rrepresents a methyl 3 th 1-1- -h carboxylic acid or lower alkoXycarbonyl, can be pre- $3 92 (4 l3 ydroxyethyl sulfonylphmyl) pyrazopared by coupling tetrazotized ammes of the general for- 1 (4' 3 h d thl lf l h l) p l (s) 3 mula carboxylic acid,

SI? Z 1- (4-fl-hydroxyethy1-sulfonylphenyl) -pyrazolone- (5 -3-carboxylic acid ethyl ester 2 i and the sulfuric acid esters of theaforementioned three f pyrazolone derivatives. Z Y (2) The new dyestuffsprepared according to the present inin which X, Y and Z have themeanings given above, with vention, which are isolated in the form ofalkali metal pyrazolone derivatives of the general formula (3) salts,preferably sodium or potassium salts and which are &

obtained with a very good yield, are very readily soluble in water. Theyare suitable for dyeing and printing various fibrous materials, forexample, wool, silk, polyamides, in particular polyhydroxylated fibrousmaterials, such as regenerated or natural cellulose, for examplecellulose, linen and cotton. The new dyestuffs are particularly suitablefor the dyeing in a long bath. They are fixed by treating the fibrousmaterial before, during or after the application of the dyestulfs bymeans of alkaline agents, such as sodium acetate, sodium bicarbonate,sodium carbonate, potassium carbonate, potassium bicarbonate sodiumhydroxide solution or trisodium phosphate.

The dyeings and prints obtained with the novel dyestuffs aredistinguished by a very good fastness to wet processing, by theirbrilliant shades and a good to very good fastness to light.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight unlessotherwise stated and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to the liter.

Example 1 17.2 parts of 4,4'-diaminodiphenyl-2,2'-disulfonic acid areneutralized and dissolved in 50 parts by volume of water with 50 partsby volume of 2 N-sodium hydroxide solution. This solution is mixed with20 parts by volume of N-sodium nitrite solution and introduced into amixture of 150 parts by volume of 2 N-hydrochloric acid and 100 parts ofice while stirring.

When the diazotization is complete the excess nitrite is removed by theaddition of amidosulfonic acid.

28.2 parts of 3-rnethyl-1-(4'-,BhydroXyethyl-sulfonylphenyl)-pyrazolone-(5) are introduced into 125parts of concentrated sulfuric acid and stirred overnight. The solutionthus obtained is stirred on 500 parts of ice and adjusted to a pH-valueof 4 by adding 120 parts of sodium carbonate. The solution obtained isthen added to the tetrazo solution prepared as described above and thepH- value is adjusted to 67 by adding sodium carbonate solution of 10%strength. When the coupling is complete, the dyestutf is precipitated bymeans of potassium chloride, filtered and dried at 50 to 60 C. There isobtained a brown-yellow powder which dissolves readily in water to givea yellow solution.

The dyestuff dyes cotton in a long bath in the presence of acid-bindingagents, such as sodium bicarbonate, sodium carbonate or trisodiumphosphate, in intense yellow shades with a very good fastness to lightand washing.

4 Example 2 31.2 parts of1-(4-B-hydroxyethyl-sulfonylphenyl)-pyrazolone-(S)-3-carboxylic acid areintroduced at room temperature in 125 parts of concentrated sulfuricacid and esterified overnight at room temperature. The solution obtainedis poured on 500 parts of ice, and the pH-value is adjusted to 4 by theaddition of 130 parts of sodium carbonate. The solution is then added tothe tetrazo solution prepared according to the method described inExample 1 and neutralized with sodium carbonate solution to a pH-valueof 67. Stirring is continued until the coupling is complete, thedyestufi is then precipitated by means of potassium chloride, filteredoff, washed and dried. The so obtained dyestutf is an orange powderwhich dissolves readily in water to given an orange-yellow solution.

When dyeing cotton or regenerated cellulose in a long bath in thepresence of acid-binding agents, with the aforementioned dyestuif,intense yellow dyeings are obtained possessing a very good fastness towet processing.

Example 3 17.2 parts of 4,4'-diaminodiphenyl-2,2'-disulfonic acid arediazotized as described in Example 1. To the tetrazo solution obtainedthere is added the solution of 28.2 parts of3-methyl-l-(4-;3-hydroxyethyl-sulfonylphenyl)-pyrazolone-(5) in 100parts by volume of water and parts by volume of 2 N-sodium hydroxidesolution and the pH-value is then adjusted to 7-8 by adding a sodiumcarbonate solution. When the coupling is complete, the disazo dyestuffis precipitated by means of sodium chloride, isolated by filtering andwashed with a sodium sulfate solution of 10% strength. After drying, thepulverized dyestuif is introduced at room temperature in 400 parts byvolume of concentrated sulfuric acid and stirred overnight. The soobtained solution is poured on 1500 parts of ice and neutralized withabout 400 parts of sodium carbonate until the pH-value 5 is attained.The dyestuff which has been esterified with sulfuric acid isprecipitated by means of potassium chloride, isolated and dried at 50 C.to C. There is obtained the same dyestutf as described in Example 1.

When replacing the 28.2 parts of 3-methyl-1-(4'-B- hydroxyethylsulfonylphenyl) pyrazolone-(S) by 31.2 parts of1-(4'-fi-hydroxyethyl-sulfonylphenyl)-pyrazolone- (5 )-3-carboxylicacid, there is obtained the same dyestuff as described in Example 2.

The following table shows further disazo dyestuffs which can be preparedin an analogous manner; it also exhibits the tints which are obtainedwhen dyeing cotton with those disazo dyestuifs:

Tetrazo component Azo component Tint on cotton OaH SIO3H (IDCHs 1 OCHB803 Yellow.

Golden-yellow.

Tetrazo component Azo component Tint on cotton HOOO SOsH

S0 11 OH:

HOOG-- Yellow.

Orange.

Yellow.

Red-orange.

Yellow.

3,313,799 9 1 10 We claim: 1. The water-soluble disazodyestuifs havingthe formula TEQ Y'NZZUR Q in which X represents a member of the groupconsisting of 15 direct linkage, O, S, SO and CH=CH--, Z represents amember of the group consisting of hydrogen, lower alkyl and loweralkoxy, Y represents a member of the group consisting of SO H and COOH,and R represents a member of the group consisting of methyl, 20 carboxyland lower alkoxy carbonyl group.

2. The water-soluble disazodyestufl having the formula 3. Thewater-soluble disazodyestuff having the formula IZHWNZZUWOH SOaH N si-CHz-CI-Iz-O-SOzH SOrCHz-CH2OSO2H 4. The water-soluble disazodyestuffhaving the formula SO H Hw MQSOP M OH3 N l I L \N 0132 S0313 HO IOrCHrCHr-O-SOgH 02--CHzCHz-O-SO:H

5. The water-soluble disazodyestufi having the formula Hooo- N=N SO,N=Nl-ooorr N IE I L \N/ on $0211 110 N/ I SOs-CHg-CHrO-SOgHSOs-CHz-CHz-O-SOgH 1 1 1 2 6. The water-soluble disazodyestufi havingthe formula SiOaH 113mm N=NO1 =1 H--om I 1! N N IIIiOI-I SO3H HO III SOgCH2-CHg-OSOsH S O2-CHzCH2O-SOaH References Cited by fih-e ExaminerUNITED STATES PATENTS 791,524- 6/1905 Witter 260-161 936,367 10/1909Schedler 260-160 2,670,265 2/1954 Heyna et a1. 26016O X 2,728,76212/1955 Heyna et a1 260195 X FOREIGN PATENTS 175,217 9/1906 Germany.

CHARLES B. PARKER, Primary Examiner.

R. J. FINNEGAN, F. D. HIGEL, Assistant Examilwrs.

1. THE WATER-SOLUBLE DISAZODYESTUFFS HAVING THE FORMULA